CN111135822B - Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound - Google Patents
Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound Download PDFInfo
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Abstract
The invention discloses an application of a supported high-dispersion noble metal catalyst in selective reaction of aromatic nitro compounds, wherein the catalyst is obtained by taking one or more than two of VIII group or IB group noble metals as active components and oxide with high specific surface area as a carrier by adopting an adsorption-rapid heat treatment method, and the content of the active components of the catalyst is 0.05-20%. The catalyst shows excellent activity, selectivity and stability for the selective hydrogenation reaction of the aromatic nitro compound. Compared with the traditional industrial synthesis route of selective hydrogenation of aromatic nitro compounds, the reaction process provided by the invention has the advantages of environmental friendliness, simplicity in operation and the like.
Description
Technical Field
The invention relates to an application of a supported high-dispersion noble metal catalyst in selective hydrogenation reaction of aromatic nitro compounds
Background
The selective hydrogenation of aromatic nitro compounds to obtain corresponding functionalized aniline compounds has important applications in many aspects, such as in the industries of dyes, pigments, medicines, pesticides, and the like. Currently, there are industrially mature techniques for the hydrogenation of simple aromatic nitro compounds, but selective reduction of nitro groups when the substituent is a reducible group remains a challenging issue. Industrially, for the selective hydrogenation of aromatic nitro compounds containing reducible groups, it is customary to employ metered amounts of reducing agents, for example Na2S2O4In order to overcome the disadvantage that the reducing agent is a hydrogen gas and PbO or H is used as the reducing agent, researchers have used a hydrogen gas as the reducing agent3PO2Added to the supported Pt catalyst, although the activity is reduced, the selectivity to the target product is improved, but such a catalyst produces phenylhydroxylamine intermediate product, which may be at a very low level at risk of explosion. Researchers find that the intermediate product can be converted into a target product by respectively adding iron salt or alum salt into the catalytic system, but a large amount of transition metal salt remains in the solution after the reaction, and the subsequent treatment process is complex and is not economical and environment-friendly. Therefore, a heterogeneous catalyst with high activity and high selectivity is urgently needed for the reaction.
Many patents and literature describe supported catalysts for the selective hydrogenation of aromatic nitro compounds, which vary in activity depending on the support and the method of preparation.
Documents 1(Science,2006,313:332) and 2(Journal of the American Chemical Society,2007,129:16230) were adopted with a deposition-precipitation methodPreparing Au/TiO by a precipitation method2The catalyst is applied to nitrobenzene hydrogenation reaction, and the gold catalyst has excellent aniline selectivity and catalytic activity for nitrobenzene compounds. At the same time, the authors have found that the reason for the high selectivity is that the nitro group of the aromatic nitro compound is preferentially adsorbed on Au and TiO2The interface of the support, and thus the nitro group, is preferentially reduced, exhibiting high selectivity.
Document 3(Advanced Synthesis)&Catalysis,2011,353:1260) prepared a porous ionic copolymer supported Pt catalyst by a one-pot method, the supported amount of Pt was 4.9 wt%, and the size of the obtained Pt nanoparticles was 2-4 nm. Under mild conditions for many substituents (R ═ F, Cl, Br, I, CHO, CN, NH)2、CH3CO, OH, etc.) exhibit high activity and selectivity.
Document 4(ACS Catalysis,2013,3:608) prepares an Rh3Ni1 catalyst by a chemical reduction method, and applies the catalyst to a selective hydrogenation reaction of an aromatic nitro compound, and the result shows that the selective reduction activity of the catalyst is good, and the corresponding amine yield of a plurality of substrates can reach 99%.
Document 5(WO 2009071727) prepared a Pt/TiO2 catalyst by impregnation at 3bar P at 40 ℃H2Under the reaction conditions of (1), when the supported amount is 0.2% in the selective hydrogenation reaction of 3-nitrostyrene, the reaction is carried out for 7 hours to obtain 92% yield and the selectivity is 93.1%.
Reference 6(Journal of Physical Chemistry C,2009,113:17803) prepared Au/Al by colloidal deposition2O3The Au nano-particle size in the catalyst is 2.5 nm. In the hydrogenation reaction of 3-nitrostyrene, the reaction conditions are 120 ℃ and 3MPa H2The pressure and the reaction time are 1h, the conversion rate is 100 percent, and the selectivity of the 3-aminostyrene reaches 99 percent. The authors concluded that the reason for the high activity of the catalyst was the small size of the Au nanoparticles and the supported Al containing acid-base sites2O3And the synergistic effect between the two is that the catalyst shows high activity and selectivity.
Disclosure of Invention
The catalyst shows high activity and selectivity in hydrogenation of aromatic nitro compounds, has mild reaction conditions, can be recycled, has good stability and low cost, and has industrial application prospect.
In order to achieve the purpose, the invention adopts the technical scheme that:
the application of a supported high-dispersion noble metal catalyst in selective reaction of aromatic nitro compounds is characterized in that the active component of the supported high-dispersion noble metal catalyst is common noble metal, a carrier is common oxide, and the mass content of the active component in the catalyst is 0.05-20%.
The preparation process of the supported high-dispersion noble metal catalyst comprises the following steps:
1) dissolving a certain amount of soluble precursor of the noble metal in a certain amount of deionized water, and adding a proper amount of common inorganic and organic reagents to obtain a noble metal precursor complex solution, wherein in order to ensure the formation of the soluble precursor complex solution of the noble metal, the ratio of the common inorganic and organic reagents to the noble metal is 10:1-1000: 1. (ii) a
The concentration of the noble metal in the noble metal precursor solution is 0.1-100 mg/ml;
the noble metal is one or a mixture of more than two of ruthenium, rhodium, palladium, silver, iridium, platinum and gold in any ratio, and the soluble precursor of the noble metal is one or more than two of chloride, nitrate and organic complex of the noble metal; the common inorganic agents are: one or a mixture of more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents in any ratio, wherein the common organic reagent is one or a mixture of more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents in any ratio.
2) The soluble precursor complex solution of the noble metal and the carrier are mixed evenly according to the required proportion, stirred for 10 to 600 minutes, filtered and dried for 8 to 12 hours at the temperature of 60 to 120 ℃ to obtain the noble metal catalyst precursor.
The carrier is one or a mixture of more than two of alumina, silicon oxide, ferric oxide, cerium oxide and titanium oxide in any ratio,
3) the catalyst is subjected to heat treatment before reaction, and is placed in He, Ar and N2、H2、O2And treating at 200-800 deg.c for 10-600 sec in air atmosphere.
The reaction is carried out in a closed high-pressure reaction kettle, the initial pressure of hydrogen in the reaction kettle at room temperature is 0.1-5Mpa, the reaction temperature is 25-120 ℃, and the reaction time is not less than 1 minute.
The reaction is carried out in a solvent, the adopted solvent is one or more than two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, pyridine, tetrahydrofuran, dodecane and water, and the concentration of the aromatic nitro compound serving as a reaction substrate in a reaction solution is 0.0001-5 mol/L;
the reaction substrate is aromatic nitro compound
The substituent R is one of hydrogen, halogen, vinyl, ethynyl, nitrile group, aldehyde group, phenolic hydroxyl, carbonyl, methyl, isopropyl, methoxyl and other aromatic nitro compound derivatives, and the number of the substituent R is 1-5.
The molar ratio of the active component of the catalyst to the reaction substrate is 1 x 10-4To 1.
The preferred reaction temperature is 20-80 deg.C, the preferred initial pressure of hydrogen in the reaction vessel at room temperature is 0.1-2.5Mp, and the preferred reaction time is 0.5-6 h.
The catalyst can be recycled for more than 2 times, the conversion rate and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.
The activity test method of the catalyst provided by the invention comprises the following steps:
the reactor is a high-pressure reaction kettle, reaction substrates, internal standards and solvents are prepared into reaction liquid with certain concentration, a certain amount of reaction liquid is taken by a pipette for reaction each time, the initial pressure of hydrogen in the reaction kettle at room temperature is 0.1-5Mpa, the reaction temperature is 25-120 ℃, and the reaction time is not less than 1 minute. After the reaction was completed, the reaction mixture was cooled to room temperature, and then a sample was taken for gas chromatography.
The invention has the following effects:
1. the selective hydrogenation of aromatic nitro compounds to obtain corresponding functionalized anilines has applications in many fields, such as agriculture, medicine, dyes and high molecular polymers. The invention provides a supported high-dispersion noble metal catalyst which can catalyze to obtain functionalized aniline with high selectivity.
2. The invention provides a supported high-dispersion noble metal catalyst which can be recycled for a plurality of times in the selective hydrogenation reaction of aromatic nitro compounds, and the activity is not obviously reduced.
3. The invention provides a supported high-dispersion noble metal catalyst which is easy to separate from a reaction solution after reaction and is simple and convenient to operate.
In a word, the invention realizes the preparation of the functionalized aniline by the high-efficiency and high-selectivity conversion of the aromatic nitro compound, and compared with the existing industrial catalyst system, the catalyst provided by the invention is green and friendly in the reaction process, saves the cost, and is expected to be applied industrially.
Drawings
FIG. 1 is an electron microscope picture of a supported high-dispersion noble metal Pt-FeOx catalyst prepared by the method of the invention.
FIG. 2 is a diagram of a supported high-dispersion noble metal Pt-CeO2HAADF-STEM pictures of the catalyst.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, but the invention is not limited thereto.
Example 1: 0.054g of chloroplatinic acid is dissolved in 20g of deionized water, 0.5g of 25% ammonia water is added, the mixture is stirred for 3 hours, 1g of ferric oxide is added, the mixture is stirred for 5 hours, filtered and washed, the obtained product is placed in a drying oven at 60 ℃ and dried for 8 hours to obtain a supported high-dispersion platinum-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated at 600 ℃ for 10 seconds under the He condition to obtain a 2% Pt/FeOx catalyst which is placed in a dryer for standby. (the catalyst is shown in the picture of an electron microscope in FIG. 1) as shown in FIG. 1: the noble metal in the catalyst of the invention exists in a form of high dispersion even atomic level dispersion, and the dispersion degree of the noble metal is 100 percent.
Example 2: 0.027g of chloroplatinic acid is dissolved in 5g of deionized water, 0.5g of ethylenediamine organic reagent is added, the mixture is stirred for 1 hour, 1g of cerium dioxide is added, the mixture is stirred for 2 hours, filtered and washed, the mixture is placed in a baking oven at 120 ℃, dried for 12 hours to obtain a supported high-dispersion platinum-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated for 120 seconds at 500 ℃ under Ar condition to obtain 1% Pt/CeO2And (5) putting the catalyst in a dryer for later use. (the catalyst is shown in the electron microscope of FIG. 2) as shown in FIG. 1: the noble metal in the catalyst of the invention exists in a form of high dispersion even atomic level dispersion, and the dispersion degree of the noble metal is 100 percent.
Example 3: dissolving 0.054g of chloroplatinic acid in 20g of deionized water, adding 1.5g of ammonium nitrate, stirring for 2h, adding 1g of aluminum oxide, stirring for 1h, filtering, washing, placing in a drying oven at 100 ℃, drying for 8h to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and adding N2After 240 seconds of treatment at 300 ℃ under the condition, 2 percent Pt/Al is obtained2O3And (5) putting the catalyst in a dryer for later use.
Example 4: dissolving 0.017g of palladium chloride in 20g of deionized water, adding 0.2g of ethanolamine organic reagent, stirring for 3H, adding 1g of ferric oxide, stirring for 4H, filtering, washing, placing in a 90 ℃ oven, drying for 10H to obtain a supported high-dispersion palladium-based catalyst precursor, placing the precursor in a quartz tube, and H2Treating at 350 deg.c for 20 sec to obtain 1% Pd/FeOx catalyst in the drier for further use.
Example 5: 0.021g of chloroauric acid is dissolved in 20g of deionized water, 0.8g of triethyl phosphate organic reagent is added, the mixture is stirred for 1 hour, 1g of cerium oxide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in an oven at 70 ℃ and dried for 7 hours to obtain a supported high-dispersion gold-based catalyst precursor, the precursor is placed in a quartz tube, the precursor is treated at 550 ℃ for 300 seconds under the air condition to obtain a 1% Au/CeO2 catalyst, and the obtained product is placed in a dryer for later use.
Example 6: dissolving 0.027g of chloroplatinic acid in 10g of deionized water, adding 2g of cysteine organic reagent, stirring for 2h, adding 1g of titanium oxide, stirring for 2, filtering, washing, placing in an oven at 80 ℃, drying for 8h to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and treating at 400 ℃ under the He condition for 120 seconds to obtain 1% Pt/TiO2And (5) putting the catalyst in a dryer for later use.
Example 7 (comparative): dissolving 0.027g chloroplatinic acid in 1.5g deionized water, adding 1g alumina, stirring for 0.5H, placing in an oven at 80 deg.C, drying for 8H, placing in a quartz tube, and placing in a quartz tube2After 600 seconds of treatment at 300 ℃ under the condition, 1 percent Pt/Al is obtained2O3And (5) putting the catalyst in a dryer for later use.
Example 8 (comparative): dissolving 0.027g chloroplatinic acid in 1.5g deionized water, adding 1g silicon oxide, stirring for 0.5H, placing in an oven at 80 deg.C, drying for 8H, placing in a quartz tube, and placing in a quartz tube2After 600 seconds of treatment at 300 ℃ under the condition, 1 percent Pt/SiO is obtained2And (5) putting the catalyst in a dryer for later use.
Application example 1:
taking a certain amount of catalyst in a reaction tube, adding 5ml of 0.1M 3-nitrostyrene reaction solution (toluene as a solvent and o-xylene as an internal standard) by a pipette, and reacting under the condition of 3bar H2(initial pressure), 40 ℃.
The specific experimental results are as follows:
results of selective hydrogenation of 3-nitrostyrene over highly dispersed noble metal catalysts loaded with iron monoxide
TABLE 2% Pt/CeO2Circulation experiment result of catalyst in selective hydrogenation reaction of 3-nitrostyrene
TABLE III results of selective hydrogenation of 1% Pt/FeOx in different reaction substrates
TABLE four results of selective hydrogenation of 3-nitrostyrene by supported highly dispersed platinum based catalysts prepared by different preparation methods
The catalyst shows excellent activity, selectivity and stability for the selective hydrogenation reaction of the aromatic nitro compound. Compared with the traditional industrial synthesis route of selective hydrogenation of aromatic nitro compounds, the reaction process provided by the invention has the advantages of environmental friendliness, simplicity in operation and the like.
Claims (8)
1. The application of the high-dispersion noble metal supported catalyst in the hydrogenation of aromatic nitro compounds is characterized in that: the catalyst is prepared by taking an oxide as a carrier and one or more than two of VIII group or IB group noble metals as active components through adsorption-rapid heat treatment, and is used in the selective hydrogenation reaction of aromatic nitro compounds;
the preparation process of the high dispersion noble metal supported catalyst is as follows,
1) dissolving a soluble precursor of noble metal in deionized water and/or an organic solvent to obtain a noble metal precursor solution, and adding an inorganic and/or organic reagent to obtain a noble metal precursor complex solution;
the concentration of the noble metal in the noble metal precursor solution is 0.1-100 mg/ml;
the volume of the deionized water and/or the organic solvent is 5ml-50 ml;
the mass of the inorganic reagent and/or the organic reagent is 0.0005g-10 g;
the noble metal soluble precursor is one or more than two of noble metal chloride, nitrate, acetylacetone complex and triphenylphosphine complex, and the inorganic reagent is: one or more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents are mixed according to any ratio, the organic reagent is one or more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents are mixed according to any ratio, and in order to ensure the formation of a soluble precursor complex solution of the noble metal, the ratio of the amounts of the inorganic and/or organic reagents and the noble metal is 10:1-1000: 1;
2) uniformly mixing the soluble precursor complex solution of the noble metal and the carrier according to the required proportion, stirring for 10-600 minutes, filtering, and drying at 60-120 ℃ for 8-12 hours to obtain a noble metal catalyst precursor;
3) the catalyst is subjected to heat treatment before reaction, and is placed in He, Ar and N2、H2、O2And reducing at 200-800 deg.c in one or several kinds of air for 10-600 sec.
2. Use according to claim 1, characterized in that: the active component is one or a mixture of more than two of ruthenium, rhodium, palladium, silver, iridium, platinum and gold in any ratio, and the mass content of the active component in the catalyst is 0.05-20%.
3. Use according to claim 1, characterized in that: the carrier oxide is one or a mixture of more than two of aluminum oxide, silicon oxide, ferric oxide, cerium oxide and titanium oxide in any ratio.
4. Use according to claim 1, characterized in that:
the reaction is carried out in a closed high-pressure reaction kettle, the initial pressure of hydrogen in the reaction kettle at room temperature is 0.1-5Mpa, the reaction temperature is 25-120 ℃, and the reaction time is not less than 1 minute.
5. Use according to claim 1 or 4, characterized in that:
the reaction is carried out in a solvent, the adopted solvent is one or more than two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, pyridine, tetrahydrofuran, dodecane and water, and the concentration of the aromatic nitro compound serving as a reaction substrate in a reaction solution is 0.0001-5 mol/L;
the reaction substrate is aromatic nitro compound
The substituent R is one, two, three, four or five of hydrogen, halogen, vinyl, ethynyl, nitrile group, aldehyde group, phenolic hydroxyl, carbonyl, methyl, isopropyl, methoxyl and other aromatic nitro compound derivatives, and the number of the substituent R is 1-5.
6. Use according to claim 1 or 4, characterized in that: the molar ratio of the active component of the catalyst to the reaction substrate is 1 x 10-4To 1.
7. Use according to claim 4, characterized in that: the reaction temperature is 20-80 ℃, the initial pressure of hydrogen in the reaction kettle is 0.1-2.5 Mpa at room temperature, and the reaction time is 0.5-6 h.
8. Use according to claim 1 or 4, characterized in that: the catalyst can be recycled for more than 2 times, the conversion rate and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.
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| CN113750995B (en) * | 2020-06-05 | 2023-09-01 | 台州学院 | Titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst and preparation method and application thereof |
| CN113751021B (en) * | 2020-06-05 | 2023-09-05 | 台州学院 | Catalyst for preparing p-aminostyrene by hydrogenation of p-nitrostyrene and preparation method and application thereof |
| CN111701589A (en) * | 2020-06-28 | 2020-09-25 | 中国科学院长春应用化学研究所 | Composite material compounded with atomic mixed grade alloy for catalyzing nitrobenzene hydrogenation, and preparation method and application thereof |
| CN113058644B (en) * | 2021-03-19 | 2022-08-26 | 山东大学 | Catalyst for catalyzing oxidative dehydrogenation and hydrogenation of organic compounds and application thereof |
| CN114471540B (en) * | 2022-02-22 | 2023-08-08 | 北京化工大学 | Sub-nanometer Pt selective hydrogenation catalyst, preparation method and application thereof |
| CN115155575B (en) * | 2022-08-03 | 2024-04-19 | 中山大学 | Double-atom catalyst for preparing aniline by efficiently catalyzing nitrobenzene hydrogenation and preparation method thereof |
| CN116212870A (en) * | 2023-01-04 | 2023-06-06 | 山东大学 | WO (WO) with double-plasma coupling enhancement 3-x -Au, and preparation method and application thereof |
| CN116078376A (en) * | 2023-01-06 | 2023-05-09 | 华南理工大学 | Supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active site, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724150A (en) * | 2005-06-16 | 2006-01-25 | 南京工业大学 | Catalyst for CO2 decomposition and preparantion process thereof |
| CN102600877A (en) * | 2012-01-11 | 2012-07-25 | 大连理工大学 | High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof |
| CN107649124A (en) * | 2016-07-25 | 2018-02-02 | 中国科学院大连化学物理研究所 | A kind of single atomic dispersion noble metal catalyst and its application |
| CN108325523A (en) * | 2018-02-02 | 2018-07-27 | 华东理工大学 | A kind of propane dehydrogenation catalyst and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0222240D0 (en) * | 2002-09-25 | 2002-10-30 | Ici Plc | Cobalt catalysts |
| CN1775351A (en) * | 2005-10-10 | 2006-05-24 | 大连理工大学 | Catalyst for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds and its use method |
| CN100531901C (en) * | 2008-05-08 | 2009-08-26 | 郴州高鑫铂业有限公司 | Preparation method of high-activity nanocrystalline platinum carbon catalyst |
| CN102000612B (en) * | 2009-09-02 | 2013-03-06 | 中国石油化工集团公司 | Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst |
| CN102247864A (en) * | 2011-05-26 | 2011-11-23 | 中国海洋石油总公司 | Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil |
| CN103819295B (en) * | 2012-11-19 | 2016-04-27 | 中国科学院大连化学物理研究所 | The application of a kind of catalyzer in aromatic nitro compound selective hydrogenation |
| CN103357422A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Carbon monoxide catalytic oxidation catalyst and preparation method thereof |
| CN107537505B (en) * | 2016-06-23 | 2019-09-10 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst, preparation method and application |
-
2018
- 2018-11-06 CN CN201811313905.9A patent/CN111135822B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724150A (en) * | 2005-06-16 | 2006-01-25 | 南京工业大学 | Catalyst for CO2 decomposition and preparantion process thereof |
| CN102600877A (en) * | 2012-01-11 | 2012-07-25 | 大连理工大学 | High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof |
| CN107649124A (en) * | 2016-07-25 | 2018-02-02 | 中国科学院大连化学物理研究所 | A kind of single atomic dispersion noble metal catalyst and its application |
| CN108325523A (en) * | 2018-02-02 | 2018-07-27 | 华东理工大学 | A kind of propane dehydrogenation catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "MnOX-CeO2/蜂窝沸石对甲苯的吸附-低温催化氧化一体化研究";刘秀珍;《中国优秀硕士学位论文全文数据库工程科技I辑》;20130515(第5期);B027-314 * |
| "Stabilizing Single-Atom and Small-Domain Platinum via Combining Organometallic Chemisorption and Atomic Layer Deposition";Liu Shengsi et al.;《ORGANOMETALLICS》;20170227;第36卷(第4期);第818-828页 * |
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